Quaternary methine compounds



United States Patent cc 3,394,130

Patented July 23, 1968 3 394 130 Z represents a chain of atoms, including C or at least QUATERNARY METIJINE COMPOUNDS 011E atom other than carbon, e.g. C and O; C and N;

James M. Straley and John G. Fisher, Kingsport, Tenn., C and S atoms, Y to complete a ring of 5 6 assignors to Eastman Kodak Company, Rochester, N.Y., members c as the 611211115 a corporation of New Jersey 5 No Drawing. Filed Oct. 4, 1965, Ser. No. 492,866 'Pheny1ene,

9 Claims. (Cl. 260-2409) -CH -O--CH CH -N]H-CH ABSTRACT OF THE DISCLOSURE Quaternary methine compound prepared by condens- 10 OCONH ing a trialkyl-2-methyleneindoline with a carbocyclic aro- 2 OCOGH (L matic aldehyde having a dicarbox'imidoalkylamino group -OH-CHr-,CHCHr, H- H2- attached thereto are useful as dyes for acrylic polymer textile material. etc. as present in e.g. succinimido, phthalimido rings and other rings given below, R1 R1 A is an acid anion such as I X\ %OCH=CHRQN /(JJ\ or, Br, 011 8041 orn@soi-, 1150;, 0113000- 11 F0 1 ZnClr, ZnBrr, etc. R I

A A The alkyl chains in the above groups are preferably lower alkyl of 1 to 4 carbon atoms.

The substituents attached to the aromatic group R to the alkyl group R and to group Z serve primarily as Thi invention relates to quaternary hi auxochrome groups to control the color of the methine pounds particularly characterized by containing a dicar- Compound and can be Varied widely to Obtain Compounds boximido radical, and textile fibers, yarns and fabrics espec y useful as teXtile y example, 2 includes dyed with the methine compounds. phenylene unsubstituted or substituted phenylene such The quaternary methine compounds have the general as y p y -a, m y p y Y- f l phenylene, e.g. o,m-methoxyphenylene, halophenylene, Y e.g. o,m-chlorophenylene; alkylsulfonamidophenylene, X R1 e.g. o,m,-methylsulfonamidophenylene; dicarboxylicacid- J R imidophenylene, e.g. o,m-succinimidophenylene; a-cyl- 1 Rs 0 amidophenylene, e.g. o,m-acetamidophenylene; benzag mid'ophenylene; thiocyanophenylene, e.g. o,m-thiocyin0- CHLOE-RP}! phenylene; alkylthiophenylene,e.g. o,m-methylthiophenyl- R4-N\ Z 40 ene; benzylaminophenylene, e.g. o,m-benzylaminophenyle o ene; N-alkylbenz-aminophenyl, e.g. o,m-N-phenylmethyl- A g ammophenylene; carbalkoxyphenylene e.g. o,m-carbethoxyphenylene; benzoylphenylene, e.g. o,m-benzoy1pheny1- ene; wherein: ical dicarboximido r i a X and Y represents either hydrogen; halogen, e.g. C1 Typ ad c 1S represented by or Br; nitro; lower alkoxy; lower alkyl; or lower carbo- O 0 alkoxy, e.g. --COOCH COOC H etc.; or X and Y taken together represent --CH=CHCH=CH- which completes a fused on monocyclic, carbocyclic, aromatic o 0" nucleus, atoms, including C or at least one atom other than carbon, e.g. C and O;

R and R are the same or dilferent lower alkyl groups g gi fi iggg a carbon Cham are e.g. as present in the 1,3,3-trimethylindolyl or 1,3-diphthalimido methyl-3-ethylindoly1 radicals, tetrachloro phthalimido R represents a monocyclic carb'ocyclic aromatic group, tetrahydro phthalimido including p-phenylene and substituted p-phenylene groups hexahydro phthalimido,

Such as given below- 4-carboxy phthalimido R represents hydrogen; lower alkyl; lower alkyl sub- 3mm) phthalimido stituted with chlorine, hydroxy, cyano, phenylcarbamoyl- 3 methy1 phthalimido Y y, or y; or 3-amino phthalimido glutarimido d bicyclo[2.2.1]-5-heptene-2,3-dicarboximido c R4--N/ \Z /CO R is a lower alkylene group straight or branch-chained, 1,8-naphthalimido e.g. ethylene, isoprop'ylene etc., citra conimido 3 4 cycl-oalkanedicarboximido e.g. analysis this product N-[2(N-ethyl-m-toluidine)ethyl]- COCH, phthalimide has the structure: o

co COCH c 2 5 o 11 ill CO I -N\ s NCH7CHN COCI-Iz C} alkyl succinimido e.g. 10 I3 1 (Jo-4311011 0 CO CH2 308 (01 N [2(N etl l t l 'd' )ethyl] g. m. iy-m-oui ine alkenyl Succlmmldo 6g 1 phthalimide above is dissolved in ml. of dimethyl- CO CH CH2CH=CHCH3 formamide by heating to about C. The solution is N cooled, and 11 ml. of phosphorus oxychloride is added, keeping the temperature below 25 C. The reaction is then heated on the steam bath for 1 hour. It is drowned Camphenmldo in 500 ml. water. The product comes down sticky but C H solidifies on standing. It is filtered off, washed with water, mom), and recrystallized from ml. of ethyl alcohol. Yield: 0 H 30.7 g., M.P. 127128.5 C. The preparation of the alde- C i hydes is further described in US. Ser. No. 252,233, filed 9,10-d1hydroanthrawne, 9,10-endo succlnlmldo Jan. 13, 1963 and US. Ser. No. 465,208 filed June 13,

H 1965. Similarly the aldehydes in which Z represents a chain /C 0-011 of atoms containing at least one atom other than carbon N 30 i.e. O, N or S, as present in the radicals: 3,5-morpho- O0CH linedione, 2,5-piperazinedione, 5,6-dihydrouracil and 2,4-

thiazolidinedione of the azo compounds described below, 11 are prepared by formylation of the corresponding aniline The methine Compounds of Formula I above are derivative. Preparations of the latter are illustrated as pared by condensing in acid solution a 1,3,3-trialkyl-2- 35 follows: methylene mdohne Wlth an aldehyde of the formula Preparation 3-[2-(N-ethyl-m-toluidino)ethyl]hydantoin 3 OCHR,N on 19.7 g. N-2-chloroethyl-Nethyl-m-toluidine, 10.0 g. R hydantoin, 13.8 g. potassium carbonate, and 150 ml. dry 4 J dimethylformamide were refluxed together for one hour. CO The reaction mixture was drowned into 500 ml. of water as illustrated in the following reaction giving a white solid on standing. The product was recrysi on z ornooorr ono1w oHlontN T 0-011 \N 0113 ll 2 CH3 oud l t CH; C16 0113 The aldehydes of the above formula where Z is a carbon chain, are prepared by reacting POCl and dimethyl formamide with 5- and 6-membered cyclic dicarboximidoalkyl aniline compounds such as disclosed in Straley et al., U.S. Patent 3,161,631 granted Dec. 15, 1964. For illustration, 89 g. (0.5 m.) of N-B-aminoethyl-N-et'hyl mtoluidine and 74 g. (0.5 m.) of phthalic anhydride are mixed intimately and heated gradually until an exothermic reaction begins. The temperature rises to C. without further heating. After the temperature begins to fall, heat is applied and held at -140 C. for 1 hour. The partially cooled melt is drowned in 500 cc. of hot ethanol and allowed to cool. The product is filtered ofi, washed with a little alcohol, and dried at 60 C. The yield is 129 g. of material melting at 86-87 C. According to tallized from ethanol to give 13.5 g. of material melting at 7677 C., having the structure:

19.7 g. N-Z-chloroethyl-N-ethyl-m-toluidine, 12.8 g. 5,5-dimethylhydantoin, 13.8 g. potassium carbonate, and

150 ml. dry dimethylformamide were refluxed together for one hour. Drowning into water, filtering, and recrystallizing from 75 ml. ethanol gave 15.2 g. white solid product with M.P. 81-82 C.

Preparation of 3-[Z-(N-ethyl-m-toluidino)ethyl]- l-methyl hydantoin 19.7 g. N-2-chloroethyl-N-ethyl-m-toluidine, 11.4 g. l-methylhydantoin, 13.8 g. potassium carbonate, and-100 ml. dry dimethylformamide were refluxed together for one hour. Drowning in water resulted in a white solid which was collected by filtration, washed with water, and recrystallized from 100 ml. ethanol to yield 18.5 g. product with M.P. 72-73 C.

Preparation of 4-[Z-(N-ethyl-m-toluidino)ethyl]- 3,5-morpholinedione 89.0 g. N-2-aminoethyl-N-ethyl-m-toluidine, 67.0 g. diglycolic acid, and 0.1 g. sulfanilic acid were heated together at 150-155 C. for one hour. The reaction mixture was poured into 500 ml. ethanol and the product allowed to crystallize. After collection by filtration and recrystallization from 500 ml. ethanol there was obtained 70.5 g. of product of M.P. 82-83 C. This material has the following structure:

Preparation of 1-[2-(N-ethyl-m-toluidino)ethyl]- 2,5 -piperazinedione 44.5 g. N-2-aminoethyl-N-ethyl-m-toluidine, 33.2 g. iminodiacetic acid, 0.1 g. sulfanilic acid were heated together at ISO-190 C. for one hour. The reaction mixture was then poured into 300 ml. ethanol and the product allowed to crystallize. Collection by filtration gave 20.0 g. product when air dried. M.P. 191-194 C. One recrystallization from ethanol gave material melting at 197.5-198.5 C. The product had the following structure:

H o-oH,

Preparation of 3-[Z-(N-ethyl-m-toluidino)ethyl] 5,6- dihydrouracil 19.7 gm. N-Z-chloroethyl-N-ethyl-m-toluidine, 11.4 g. 5,6-dihydrouracil, 13.8 g. potassium carbonate, and 100 ml. dry dimethylformarnide were refluxed together for one hour. The reaction mixture was drowned into Water, and the product collected by filtration, washed with water, and recrystallized from 50% aqueous ethanol. Yield: 20.5 g., M.P. 108-110 C. The product has the following structure:

6 Preparation of 3 [2-(N-ethyl-m-toluidino ethyl] 2,4- thiazolidinedione 19.7 g. N-Z-cIoroethyI-N-ethyl-m-toluidine, 11.7 g. 2,4- thiazolidinedione, 13.8 g. potassium carbonate, and 100 ml. dry dimethylformamide were heated together at 130 C. for one hour. Drowning of the reaction mixture into water gave a yellow oil, which was washed by decantation and taken up in 100 mil. ethanol. The product crystallized when alcohol solution was chilled. There was Obtained 10.0 g. of product after filtering and drying in air. M.P. 59-60 C.

The 1,3,3-trimethyl-2-methylene indolines are compounds well-known in the art.

The quaternary compounds are especially useful as dyes for acrylic polymer textile materials such as those containing acrylonitrile units yielding dyeings having a variety of colors and having good fastness, for example, to washing, light, gas (atmospheric fumes), and sublimation. The azo compounds can also be expected to respond favorably to other tests as textile dyes described in A.A.T.C.C. Technical Manual, 1964 edition. The degree of utility can be expected to vary depending in part upon the textile material being dyed and the formula of the particular quaternary compound in use. Thus, generally all of the quarternary compounds will not have the same degree of utility for the same textile material.

The quaternary indole methine compounds of the invention exhibit substantially better dyeing and fastness properties such as light-fastness, than do similar quaternary methine compounds such as CH3 I on.

CHQCH: CH=CH N\ CH CH 01 oh. Cl on. 2 a

The following example illustrates one way in which the methine compounds of the invention can be used to dye acrylonitrile polymer textile material. .1 gram of dye is dissolved by warming in 5 cc. of methyl Cellosolve. A 2% aqueous solution of a nonionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product) is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. 5 cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and in the case of Orlon 42 the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

Representative acrylonitrile polymer textile fibers, yarns and fabrics dyed by the azo compounds include those polymers containing at least about 35% combined acrylonitrile units and up to about acrylonitrile units, and modified, for example, by 85-5% of vinyl pyridine units as described in U.S. Patents 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified 'by 65-5% of vinylpyrrolidone units, for example, as described by U.S. Patent 2,970,783, or modified with 65-5% acrylic ester or acrylamide units as described in U.S. Patents 2,879; 253; 2,879,254 and 2,838,470. Similar amounts of the other polymeric modifiers mentioned above are also usein].

A preferred group of copolymers are the modacrylic polymers such as described in U.S. Patent 2,831,826 composed of :a mixture of (A) 70-95% by weight of a copolymer of from 30 to 65% by weight of vinylidene chloride or vinyl chloride and 70-35% by weight of acrylonitrile, and (B) 30-5 by weight of a second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

A particularly efficacious group of modacrylic polymers is an acetone soluble mixture of (A) 70-95% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30- -by weight of an acrylamide homopolymer having the above formula wherein R R and R are as described above. Specific polymers of that group contain 70-95% by Weight of (A) a copolymer of from 30-65% by weight of vinylidene chloride and 70-35% by weight of acryl-onitrile and (B) 30-5% by weight of a lower N-alkylacrylamide polymer such as poly-N-methylacrylamide, poly-N- isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following examples will serve to illustrate our invention.

EXAMPLE 1 CzH CN O ZnClg 2 C16 0 EXAMPLE 2 Thet aldehyde in Example 1 is replaced by 2.99 g. of 4(N,/3-cyanoethyl-N,/3-succinimidoethylamino)benzaldehyde to obtain 5.0 g. of a dye which imparts fast scarlet shades to acrylic fibers. This dye has the following structure.

onnoN g CH=CHN /o-or-r2 4 0mm I CCH2 2.01, 2 ()1 0 EXAMPLE3 A solution of 3.7 g. of 4(N,N-diB-succinimidoethylamino)benzaldehyde and 1.73 g. of 1,3,3-trimethyl-2- methylene indoline in ml. of acetic acid was heated on the steam bath for four hours. The red solution was drowned in 1 l. of water and the dye precipitated by addition of solid NaI with good stirring. The dye was collected on a funnel, Washed with ml. of water and dried at 8 40 C. This dye imparts fast yellowish-red shades to acrylic fibers and has the following structure.

CH3 0 CH3 II /CCH2 g CH=CH@N GZH4N\ I a I o z EXAMPLE4 The indoline in Example 1 is replaced by 2.08 g. of 1,3,3-trimethyl-2-methylene-5-chloroindoline, to obtain 5.3 g. of the following dye. This dye imparts fast bluish-red o shades to acrylic fibers.

01- CHQ CH3 /C2H4CN (I) e GH=CH N L-CH1 C2H4N 4 CH3 c-oHi 211201, C19 ll EXAMPLE 5 The aldehyde in Example 1 is replaced by 4.6 g. of 4(N,N di fi-phthalimidoethylamino)-o-tolualdehyde to obtain 6.02 g. of the following dye.

Into a 300 ml. 3-necked flask equipped with a stirrer, thermometer, and condenser was placed a mixture of 10.38 grams (0.06 mole), 1,3,3-trimethyl-2-methylene indoline, 18.79 grams (0.06 mole), 4-([N-(fl-cyanoethyl)- N-(B-succinimidoethyl) ]amino-2-methybenzaldehyde, and 126 grams ml.] of acetic acid. The mixture Was heated slowly to 90-95 C. and held there for 4 hours. The reaction mixture was then drowned into 1000 grams of 1015 C. water followed by the addition of 12.0 grams [0.074 mole] of zinc sulfate, grams of 93% sulfuric acid, and 200 grams of anhydrous sodium sulfate, the latter being added over a 20 minute period to avoid lumping. The mixture was stirred for one hour, filtered, and the dye dried at 60 C. The dye, giving fast red shades on acrylic fibers, has the following formula:

0mm CH3 sonr CH3 Methine compounds containing the other anions A described above are obtained by use in Example 1 process of the appropriate acid such as phosphoric or p-toluenesulfonic acids in place of hydrochloric acid.

Additional methine compounds having Formula I above are prepared in the manner described in Example 1 by reacting the appropriate indoline and aldehyde indicated in the following table.

Substituent on Color on R R1 p-phenylene R; Z Acrylic radical R Fibers CH CH5 III-CH3 CgH4C1 -CHgCHz Bluish red.

CH3 CH3 III-CH CzH4CN -CHz--CHg- DO. CH3 CH3 m-CH; CgHCN -CHz-CH: Red violet.

H CH m-CH; CzH4CN -CH CH2 Red. CH CH3 III-CH3 C1H4CN CHg-CHz- Bluish red. C7Hl5 CH3 m-CH; -CgH4CN -CHgCHz- Red. H CH3 CH3 Ill-CH3 CREE CHgCHz- Bluish red.

' 13 H H CH CH3 m-CH; 04m Do.

CE: 14 H H CH3 CH3 In-CH --CHn --!CH CH: D0.

-CH CH2 CH9 h) 15 H H CH3 CH3 m-CH: -CzH CNH@ --OH;OH Red.

Cl H CH3 CH3 Ill-CH --CHg-CHCH3CI -CHzCH9-- Red. H CH CH Ill-CH3 CzH4CN -CHzO CHr- Red. H CH3 CH3 Ill-CH -CzH4Cl CH:NHOH2 Red. H CH3 CH H -C2H5 -CH:CHzCHz- Orange red. H CH; CH3 III-CH3 --CzH NH-CHzCH2- ed. H CH OH: H CH CH -SO -CH: Orange red.

CH CHa CH Ill-CH3 ---CzH4C1 Bluish red.

23 01 OH; 0H, CH3 111-0113 -o2HtoN Do.

24 01 on, om CH3 m-OHa C:H4CN Red.

25 -CH=CH--CH=CH- CH3 CHa CH3 -C2H4C1 --CzH4- Red violet. 26 i. -CH=CH-CH=CH CH3 CH3 CH3 --C2H4Cl D0.

H CH3 CH3 CH3 CH:CHOH CHgCHz- Red. H CH CH CH -CHgCHzOCOCH CH2CH2- Red. H CH CH CH CHgCHgO CH3 CHzCHz- Red. H CH CH3 CH3 H CH2CH2- Red. H CH3 CH3 O-CHa C3H4CN CH2CH2- Red. H CH3 m-CH3 C2H4CN CH2CH2- Red.

2 a H CH3 CH II1-O CH3 CzH4CN --CHgCHz Red. H CH3 CH3 O-Cl --C2H4CN -CHzCH2- Red.

Although the invention has been described in considerable detail with particular reference to certain preferred wherein:

embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

We claim:

1. A quaternary methine compound having the formula X and Y each represents hydrogen, chlorine, bromine,

nitro, lower alkoxy, lower alkyl, or lower carboalkoxy, or X and Y taken together represent carbamoyloxyalkyl, lower methoxyalkyl, lower acetoxyalkyl, or

In R represents lower alkylene;

A represents an acid anion. 2. A quaternary methine compound having the formula wherein:

R represents ethylene or isopropylene;

Z represents ethylene, propylene, isopropylene, vinylene, methylvinylene, o-phenylene, -tetrachloro-0- phenylene, nitro-o-phenylene, methyl-o-phenylene, amino-o-phenylene, tetrahydro-o-phenylene, 1,2-cyclohexylene, bicyclo[2.2.1] 5 heptene 2,3-ylene, CH OCH CH NHCH -NHCH CH CH SO CH2, -NHCH NHC( CH "N(CH3)CHZ' 70 OH (I CONllphunyl l I -cuC1n-, -CllCllr-, or -C1IOHi- A represents an acid anion.

and

3. A quaternary methine compound having the formula wherein X represents hydrogen or chlorine;

R represents p-phenylene or methyl-p-phenylene;

Z represents ethylene, propylene, vinylene, or o-phenylene; and

A represents an acid anion.

4. A compound according to claim 3 wherein:

Z represents ethylene or o-phenylene; and

A represents a chloride, iodide or sulfate ion.

5. A quaternary compound of the formula wherein A is an acid anion.

6. A quaternary compound of the formula clmoN o u es cu=cir- N CCH:

c n N/ on; A a

wherein A is an acid anion.

7. A quaternary compound of the formula CH3 Cl CH3 /C2H4CN fl) ea CH=CH- N 041m I 6 C2H4N CH3 A om wherein A is an acid anion.

8. A quaternary compound of the formula CH; O I cm /CCH2 o -CH=CHAN C2H4N C CH cm A 2 wherein A is an acid anion.

13 14 9. A quaternary compound of the formula References Cited CH3 5 UNITED STATES PATENTS I CH3 C 5 2,850,520 10/1958 Merian et 211. CH=CH -N CH4N f HENRY R. JILES, Primary Examiner. CH3 A9 H. I. MOATZ, Assistant Examiner.

wherein A is an acid anion. 10 

